8-hydroxy ether quinoline derivatives

ABSTRACT

A process for the protection of cultivated plants against harmful effects of aggressive agricultural chemicals by the use of compounds of the formula I    &lt;IMAGE&gt;  (I)  wherein R1, R2 and R3 independently of one another are each hydrogen, halogen, C1-C3-alkyl, C1-C3-alkoxy, nitro or cyano, R4, R5 and R6 independently of one another are each hydrogen, halogen or C1-C3-alkyl, A is any one of the groups -CH2-, -CH2-CH2- or -CH(CH3)-, and Z is cyano, or amidoxime which can be acylated on the oxygen atom, including acid addition salts and metal complexes thereof.

This is a divisional of application Ser. No. 465,740, filed on Feb. 11, 1983, U.S. Pat. No. 4,623,727, issued Nov. 18, 1986.

The present invention relates to the use of quinoline derivatives for the protection of cultivated plants against harmful effects of aggressive agricultural chemicals, to compositions containing these quinoline derivatives, to novel quinoline derivatives, and to the production thereof.

With the use of aggressive agricultural chemicals, such as plant protection products, especially herbicides, the cultivated plants frequently suffer damage which is not insignificant. In order to overcome this problem, there have already been suggested compositions which are intended to lessen or prevent these unfavourable effects on the cultivated plants. Plant protection compositions containing nitrile and oxime derivatives of aryloxyalkanecarboxylic acids have thus been described in the German Offenlegungsschrift No. 3,000,076.

It has now been found that surprisingly a group of quinoline derivatives is excellently suitable for protecting cultivated plants against the harmful effects of aggressive agricultural chemicals, for example plant protective compositions, particularly herbicides. These quinoline derivatives are denoted in the following by the term "antidote".

Quinoline derivatives which are suitable for protecting cultivated plants against the harmful effects of aggressive agricultural chemicals correspond to the formula I ##STR2## wherein R₁, R₂ and R₃ independently of one another are each hydrogen, halogen, C₁ -C₃ -alkyl, C₁ -C₃ -alkoxy, nitro or cyano,

R₄, R₅ and R₆ independently of one another are each hydrogen, halogen or C₁ -C₃ -alkyl,

A is a group --CH₂ --, --CH₂ --CH₂ -- or --CH(CH₃)--, and

Z is cyano or amidoxime which can be acylated on the oxygen atom,

including acid addition salts and metal complexes thereof.

By amidoxime is meant the group ##STR3## The amidoxime can be acylated on the oxygen atom. Amidoximes acylated on the oxygen atom are those of the formula ##STR4## in which E is --R₇, --OR₈, --SR₉ or --NR₁₀ R₁₁, where R₇ is C₁ -C₇ -alkyl which is unsubstituted or is substituted by halogen or C₁ -C₄ -alkoxy, or R₇ is C₃ -C₆ -cycloalkyl, C₂ -C₄ -alkenyl, phenyl which is unsubstituted or substituted by halogen, nitro or C₁ -C₃ -alkyl, or it is benzyl which is unsubstituted or substituted by halogen, nitro or C₁ -C₃ -alkyl, or R₇ is a 5- or 6-membered heterocyclic ring which contains one or two hetero atoms from the group N, O and S, and which is unsubstituted or substituted by halogen; and R₈, R₉ and R₁₀ independently of one another are each C₁ -C₈ -alkyl which is unsubstituted or substituted by halogen, or each are C₂ -C₄ -alkenyl, C₃ -C₆ -alkynyl, phenyl which is unsubstituted or substituted by halogen, C₁ -C₃ -alkyl, C₁ -C₃ -alkoxy, trifluoromethyl or nitro, or they are each benzyl which is unsubstituted or substituted by halogen or nitro, R₁₁ is hydrogen, C₁ -C₈ -alkyl or C₁ -C₃ -alkoxy, or R₁₀ and R₁₁ together with the nitrogen atom to which they are bound form a 5- or 6-membered heterocyclic radical which can contain a further hetero atom from the group N, O and S.

As a heterocyclic ring, R₇ can be a saturated, partially saturated or unsaturated heterocyclic compound, for example thiophene, furan, tetrahydrofuran and pyrimidine.

Heterocyclic radicals which are formed by R₁₀ and R₁₁ jointly with the nitrogen atom to which they are bound are saturated, partially saturated or unsaturated heterocyclic radicals. Examples of such heterocyclic radicals are: pyrrolidine, pyrroline, pyrrole, imidazolidine, imidazoline, imidazole, piperazine, pyridine, pyrimidine, pyrazine, thiazine, oxazole, thiazole and particularly piperidine and morpholine.

Suitable as salt formers are organic and inorganic acids. Examples of organic acids are: acetic acid, trichloroacetic acid, oxalic acid, benzenesulfonic acid and methanesulfonic acid; and examples of inorganic acids are: hydrochloric acid, hydrobromic acid, hydriodic acid, sulfuric acid, phosphoric acid, phosphorous acid and nitric acid.

Suitable metal-complexing agents are for example: elements of the 3rd and 4th main groups, such as aluminium, tin and lead, as well as of the 1st to 8th subgroups, such as chromium, manganese, iron, cobalt, nickel, zirconium, zinc, copper, silver and mercury. The subgroup elements of the 4th period are preferred.

Halogen, as substituent or part of a substituent, is in this case fluorine, chlorine, bromine or iodine.

Alkyl, as substituent or part of a substituent, embraces, within the limits of the stated number of carbon atoms, all straight-chain and all branched-chain alkyl groups.

C₃ -C₆ -cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

To be mentioned among the C₂ -C₄ -alkenyl and C₃ -C₆ -alkynyl groups are in particular: vinyl, allyl, 1-propenyl, isopropenyl and propynyl.

Particularly suitable for application according to the invention are compounds of the formula I in which R₁, R₂ and R₃ independently of one another are each hydrogen, halogen, C₁ -C₃ -alkyl, C₁ -C₃ -alkoxy, nitro or cyano; R₄, R₅ and R₆ independently of one another are each hydrogen, halogen or C₁ -C₃ -alkyl; A is any one of the groups: --CH₂ --, --CH₂ --CH₂ or --CH(CH₃)--; and Z is cyano or one of the groups ##STR5## wherein E is --R₇, --OR₈, --SR₉ or --NR₁₀ R₁₁, where R₇ is C₁ -C₇ -alkyl which is unsubstituted or substituted by halogen or C₁ -C₄ -alkoxy, or R₇ is C₃ -C₆ -cycloalkyl, C₂ -C₄ -alkenyl, phenyl which is unsubstituted or substituted by halogen, nitro or C₁ -C₃ -alkyl, or it is benzyl which is unsubstituted or substituted by halogen, nitro or C₁ -C₃ -alkyl, or R₇ is a 5- or 6-membered heterocyclic ring which contains one or two hetero atoms from the group N, O and S, and which is unsubstituted or substituted by halogen, R₈, R₉ and R₁₀ independently of one another are each C₁ -C₈ -alkyl which is unsubstituted or substituted by halogen, or each are C₂ -C₄ -alkenyl, C₃ -C₆ -alkynyl, phenyl which is unsubstituted or substituted by halogen, C₁ -C₃ -alkyl, C₁ -C₃ -alkoxy, trifluoromethyl or nitro, or each are benzyl which is unsubstituted or substituted by halogen or nitro, R₁₁ is hydrogen, C₁ -C₈ -alkyl or C₁ -C₃ -alkoxy, or R₁₀ and R₁₁ jointly with the nitrogen atom to which they are bound form a 5- or 6-membered heterocyclic radical which can contain a further hetero atom from the group N, O and S; including acid addition salts and metal complexes thereof.

Preferred of these compounds are those wherein R₁ is hydrogen, chlorine, bromine, iodine or nitro; R₂ is hydrogen; R₃ is hydrogen, fluorine, chlorine, bromine, iodine, C₁ -C₃ -alkyl or nitro; R₄ is hydrogen, bromine or methyl; R₅ is hydrogen; R₆ is hydrogen or methyl; A is --CH₂ --, --CH₂ --CH₂ -- or --CH(CH₃)--; and Z is cyano, ##STR6## wherein E is --R₇, --OR₈, --SR₉ or --NR₁₀ R₁₁, where R₇ is C₁ -C₇ -alkyl, C₁ --C₃ -alkyl which is substituted by 1 to 3 chlorine or bromine atoms, or it is C₁ -C₄ -alkoxymethyl, C₃ -C₆ -cycloalkyl, C₂ -C₃ -alkenyl, phenyl which is unsubstituted or substituted by one or two substituents from the group chlorine, nitro and methyl, or it is benzyl which is unsubstituted or monosubstituted by chlorine or nitro, or it is a thiophene, furan, tetrahydrofuran or pyrimidine ring each of which is unsubstituted or mono- or disubstituted by chlorine or bromine, R₈ is C₁ -C₄ -alkyl, ethyl which is monosubstituted by chlorine or bromine, or it is C₂ -C₃ -alkenyl, propynyl, phenyl which is unsubstituted or monosubstituted by nitro, or it is benzyl which is unsubstituted or monosubstituted by nitro, R₉ is C₁ -C₇ -alkyl, R₁₀ is C₁ -C₄ -alkyl, chloroethyl, or phenyl which is unsubstituted or substituted by one or two substituents from the group chlorine, methoxy or trifluoromethyl, and R₁₁ is hydrogen, methyl or methoxy, or R₁₀ and R₁₁ jointly with the nitrogen atom to which they are bound form a piperidine or morpholine ring.

More especially preferred is the use of compounds of the formula I wherein R₁ is hydrogen, chlorine, bromine or iodine; R₂ is hydrogen; R₃ is hydrogen, chlorine or nitro; R₄ and R₅ are hydrogen; R₆ is hydrogen or methyl; A is --CH₂ --, --CH₂ --CH₂ -- or --CH(CH₃)--; and Z is cyano, ##STR7## wherein E is --R₇, --OR₈, --SR₉ or --NR₁₀ R₁₁, where R₇ is methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, chloromethyl, bromomethyl, 2-chloroethyl, 3-chloro-n-propyl, 1,2-dichloroethyl, methoxymethyl, n-propoxymethyl, sec-butoxymethyl, cyclopropyl, vinyl, 1-propenyl, isopropenyl, phenyl, 2-chlorophenyl, 4-chlorophenyl, benzyl, 2-thienyl, 2-furyl, 5-bromo-2-furyl, 2-tetrahydrofuryl or 2,4-dichloropyrimidin-5-yl, R₈ is methyl, ethyl, n-propyl, n-butyl, 2-bromoethyl, allyl, phenyl or benzyl, R₉ is ethyl, isopropyl or n-pentyl, R₁₀ is methyl, ethyl, isopropyl, n-butyl, phenyl, 3-trifluoromethylphenyl, 4-chlorophenyl or 2,5-dichlorophenyl, and R₁₁ is hydrogen or methoxy.

Compounds of this group to be particularly emphasised are those wherein R₁ is hydrogen, chlorine, bromine or iodine; R₂ is hydrogen; R₃ is hydrogen or chlorine; R₄ and R₅ are hydrogen; R₆ is hydrogen or methyl; A is --CH₂ --; and Z is cyano, ##STR8## wherein E is R₇, --OR₈ or --NR₁₀ R₁₁, where R₇ is chloromethyl, R₈ is methyl, R₁₀ is isopropyl, and R₁₁ is hydrogen.

Individual compounds to be preferably used are:

8-(cyanomethoxy)-quinoline,

2-(8-quinolinoxy)-acetamide oxime,

2-methyl-8-(cyanomethoxy)-quinoline,

2-(2-methyl-8-quinolinoxy)-acetamide oxime,

2-(5-chloro-8-quinolinoxy)-acetamide oxime,

O-(isopropylaminocarbonyl)-2-(8-quinolinoxy)-acetamide oxime,

5-chloro-7-bromo-8-(cyanomethoxy)-quinoline,

O-(chloromethylcarbonyl)-2-(8-quinolinoxy)-acetamide oxime,

2-(5-chloro-7-bromo-8-quinolinoxy)-acetamide oxime,

2-(5-chloro-7-iodo-8-quinolinoxy)-acetamide oxime,

O-(isopropylaminocarbonyl)-2-(5-chloro-7-bromo-8-quinolinoxy)-acetamide oxime,

2-(2-methyl-5,7-dichloro-8-quinolinoxy)-acetamide oxime,

5,7-dichloro-8-(cyanomethoxy)-quinoline,

O-(isopropylaminocarbonyl)-2-(5-chloro-7-iodo-8-quinolinoxy)-acetamide oxime,

2-methyl-5,7-dichloro-8-(cyanomethoxy)-quinoline,

O-(isopropylaminocarbonyl)-2-(2-methyl-5,7-dichloro-8-quinolinoxy)-acetamide oxime;

and in particular:

5-chloro-7-iodo-8-(cyanomethoxy)-quinoline,

5-chloro-8-(cyanomethoxy)-quinoline, and

O-(methoxycarbonyl)-2-(8-quinolinoxy)-acetamide oxime.

Aggressive agricultural chemicals are for example: defoliating agents, desiccants, agents for protection against frost damage, and plant protection products, for example insecticides, fungicides, bactericides, nematocides and especially herbicides. The agricultural chemicals can belong to various classes of substances. Herbicides can belong for example to one of the following classes: triazines and triazinones; ureas, for example 1-(benzothiazol-2-yl)-1,3-dimethylurea ("Methabenzthiazuron"), or in particular phenylureas or sulfonylureas; carbamates and thiocarbamates; haloacetanilides, especially chloroacetanilides; chloroacetamides; halophenoxyacetic acid esters; diphenyl ethers, such as substituted phenoxyphenoxyacetic acid esters and -amides, and substituted phenoxyphenoxypropionic acid esters and -amides; substituted pyridyloxyphenoxyacetic acid esters and -amides and substituted pyridyloxyphenoxypropionic acid esters and -amides, particularly 2-[4-(3,5-dichloropyridyl-2-oxy)phenoxy]-propionic acid-2-propynyl ester and 2-[4-(5-trifluoromethylpyridyl-2-oxy)-phenoxy]-propionic acid-n-butyl ester; benzoic acid derivatives; nitroanilines; oxadiazolones; phosphates; and pyrazoles.

The substances specified below are examples of those coming into consideration:

triazines and triazinones: 2,4-bis(isopropylamino)-6-methylthio-1,3,5-triazine ("Prometryne"), 2,4-bis(ethylamino)-6-methylthio-1,3,5-triazine ("Simetryne"), 2-(1',2'-dimethylpropylamino)-4-ethylamino-6-methylthio-1,3,5-triazine ("Dimethametryne"), 4-amino-6-tert-butyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one ("Metribuzin"), 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine ("Atrazine"), 2-chloro-4,6-bis(ethylamino)-1,3,5-triazine ("Simazine"), 2-tert-butylamino-4-chloro-6-ethylamino-1,3,5-triazine ("Terbuthylazine"), 2-tert-butylamino-4-ethylamino-6-methoxy-1,3,5-triazine ("Terbumeton"), 2-tertbutylamino-4-ethylamino-6-methylthio-1,3,5-triazine ("Terbutryne"), 2-ethylamino-4-isopropylamino-6-methylthio-1,3,5-triazine ("Ametryne");

ureas: 1-(benzothiazol-2-yl)-1,3-dimethylurea; phenylureas, for example 3-(3-chloro-p-tolyl)-1,1-dimethylurea ("Chlortoluron"), 1,1-dimethyl-3-(ααα-trifluoro-m-tolyl)urea ("Fluometuron"), 3-(4-bromo-3-chlorophenyl)-1-methoxy-1-methylurea ("Chlorbromuron"), 3-(4-bromophenyl)-1-methoxy-1-methylurea ("Metobromuron"), 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea ("Linuron"), 3-(4-chlorophenyl)-1-methoxy-1-methylurea ("Monolinuron"), 3-(3,4-dichlorophenyl)-1,1-dimethylurea ("Diuron"), 3-(4-chlorophenyl)-1,1-dimethylurea ("Monuron"), 3-(3-chloro-4-methoxyphenyl)-1,1-dimethylurea ("Metoxuron"); sulfonylureas, for example N-(2-chlorophenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(4,6-dimethylpyrimidin-2-yl)-urea, N-(2,5-dichlorophenylsulfonyl)-N'-(4,6-dimethoxypyrimidin-2-yl)-urea, N-[2-(2-butenyloxy)-phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea, and also the sulfonylureas mentioned in the European Patent Publications Nos. 44808 and 44809;

carbamates and thiocarbamates: N-(3',4'-dichlorophenyl)propionanilide ("Propanil"), S-4-chlorobenzyl-diethylthiocarbamate ("Benthiocarb"), S-ethyl-N,N-hexamethylenethiocarbamate ("Molinate"), S-ethyl-dipropyl-thiocarbamate ("EPTC"), N,N-di-sec-butyl-S-benzyl-thiocarbamate, S-(2,3-dichlorallyl)-di-isopropyl-thiocarbamate ("Di-allate"), 1-(propylthiocarbonyl)-decahydro-quinaldine, S-ethyl-di-isobutyl-thiocarbamate ("Butylate");

chloroacetanilides: 2-chloro-2',6'-diethyl-N-(2"-n-propoxyethyl)-acetanilide ("Propalochlor"), 2-chloro-6'-ethyl-N-2"-methoxy-1"-methylethyl)-acet-o-toluidide ("Metolachlor"), 2-chloro-2',6'-diethyl-N-(butoxymethyl)acetanilide ("Butachlor"), 2-chloro-6'-ethyl-N-(ethoxymethyl)acet-o-toluidide ("Acetochlor"), 2-chloro-6'-ethyl-N-(2"-propoxy-1"-methylethyl)acet-o-toluidide, 2-chloro-2',6'-dimethyl-N-(2"-methoxy-1"-methylethyl)acetanilide, 2-chloro-2',6'-dimethyl-N-(2"-methoxyethyl)acetanilide ("Dimethachlor"), 2-chloro-2',6'-diethyl-N-(pyrazol-1-ylmethyl)acetanilide, 2-chloro-6'-ethyl-N-(pyrazol-1-ylmethyl)acet-o-toluidide, 2-chloro-6'-ethyl-N-(3,5-dimethylpyrazol-1-ylmethyl)acet-o-toluidide, 2-chloro-6'-ethyl-N-(2"-butoxy-1"-methylethyl)acet-o-toluidide ("Metazolachlor"), 2-chloro-6'-ethyl-N-(2"-butoxyl-1"-(methylethyl)-acet-o-toluidide and 2-chloro-2'-trimethylsilyl-N-(butoxymethyl)acetanilide;

chloroacetamides: N-[1-isopropyl-2-methylpropen-1-yl-(1)]-N-(2'-methoxyethyl)-chloroacetamide;

diphenyl ethers and nitrodiphenyl ethers: 2,4-dichlorophenyl-4'-nitrophenyl ether ("Nitrofen"), 2-chloro-1-(3'-ethoxy-4'-nitrophenoxy)-4-trifluoromethyl-benzene ("Oxyfluorfen"), 2',4'-dichlorophenyl-3-methoxy-4-nitrophenyl ether ("Chlormethoxynil"), 2-[4'-(2",4"-dichlorophenoxy)phenoxy)-propionic acid-methyl ester, N-(2'-phenoxyethyl)-2-[5'(2"-chloro-4"-trifluoromethylphenoxy)-phenoxy]-propionic acid amide, 2-[2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)phenoxy]-propionic acid-2-methoxyethyl ester; 2-chloro-4-trifluoromethylphenyl-3'-oxazolin-2'-yl-4'-nitrophenyl ether;

benzoic acid derivatives: methyl-5-(2',4'-dichlorophenoxy)-2-nitrobenzoate ("Bifenox"), 5-(2'-chloro-4'-trifluoromethylphenoxy)-2-nitrobenzoic acid ("Acifluorfen"), 2,6-dichlorobenzonitrile ("Dichlobenil");

nitroanilines: 2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline ("Trifluralin"), N-(1'-ethylpropyl)-2,6-dinitro-3,4-xylidine ("Pendimethalin");

oxadiazolones: 5-tert-butyl-3-(2',4'-dichloro-5'-isopropoxyphenyl)-1,3,4-oxadiazol-2-one ("Oxadizon");

phosphates: S-2-methylpiperidino-carbonylmethyl-O,O-dipropylphosphorodithioate ("Piperophos"); and

pyrazoles: 1,3-dimethyl-4-(2',4'-dichlorobenzoyl)-5-(4'-tolylsulfonyloxy)-pyrazole.

The compounds of the formula I are particularly suitable for protecting cultivated plants against harmful effects of herbicides of the formula A ##STR9## wherein X"₁ is hydrogen or halogen,

X"₂ is hydrogen, halogen or trifluoromethyl,

Q is the fragment ═N-- or ═CH--,

R" is C₁ -C₄ -alkyl which is unsubstituted or substituted by C₁ -C₄ -alkoxy, or it is C₃ -C₄ -alkenyl, C₃ -C₄ -alkynyl or ##STR10## where R₁₃ is C₁ -C₄ -alkyl, R₁₄ is C₁ -C₄ -alkyl, or R₁₃ and R₁₄ together are C₁ -C₅ -alkylene.

Cultivated plants which can be protected by quinoline derivatives of the formula I against aggressive agricultural chemicals are in particular those which are of importance in the foodstuffs and textile fields, for example cultivated millet, rice, maize, varieties of cereals (wheat, rye, barley, oats, and so forth), cotton, sugar beet, sugar cane and soya bean.

A suitable process for protecting cultivated plants by the use of compounds of the formula I comprises treating cultivated plants, parts of these plants, or soils intended for the cultivation of the cultivated plants, before or after introduction of the vegetable material into the soil, with a compound of the formula I or with a composition containing such a compound. The treatment can be carried out before, simultaneously with or after the application of the agricultural chemicals. Parts of plants concerned are especially those which are capable of the new formation of a plant, for example seeds, fruits, stems and branches (cuttings), as well as roots, tubers and rhizomes.

The invention relates also to a process for the selective controlling of weeds in crops of cultivated plants, in which process the cultivated plants, parts of the cultivated plants, or cultivated areas for cultivated plants, are treated with a herbicide and a compound of the formula I or Ia, or with a composition containing this combination. The compositions which contain the herbicide/antidote combination likewise form subject matter of the present invention.

The weeds to be controlled can be both monocotyledonous and dicotyledonous weeds.

Cultivated plants or parts of these plants to be protected are for example those mentioned in the foregoing. The cultivated areas concerned are those on which cultivated plants are already growing, or sown areas of land, and also the soil intended for the growing of cultivated plants.

The amount of antidote to be applied in proportion to the amount of agricultural chemical depends largely upon the type of application. In the case of a field treatment, which is carried out either with the use of a tank mixture or with a separate application of agricultural chemical and antidote, the employed ratio of antidote to agricultural chemical is as a rule from 1:100 to 10:1, preferably 1:5 to 8:1, and particularly 1:1.

With seed dressing and similar methods of application, however, the amounts of antidote required in proportion to the amounts of agricultural chemical applied per hectare of cultivated land are much smaller. There are used for seed dressing as a rule 0.1 to 10 g of antidote per kg of seed, preferably 1 to 2 g. When the antidote is applied shortly before sowing, with seed swelling, there are advantageously used antidote solutions containing the active ingredient at a concentration of 1 to 10,000 ppm, preferably 100 to 1000 ppm.

The compounds of the formula I can be used on their own or together with inert additives and/or the agricultural chemicals to be antagonised.

The present application relates therefore also to compositions which contain compounds of the formula I and inert additives and/or agricultural chemicals to be antagonised, especially plant protection agents, in particular herbicides.

For application, the compounds of the formula I, or combinations of compounds of the formula I with the agricultural chemicals to be antagonised, are advantageously used together with auxiliaries customarily employed in formulation practice, and are thus processed, in a known manner, for example into the form of emulsion concentrates, brushable pastes, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusts or granulates, and also encapsulations in for example polymeric substances. The application processes, such as spraying, atomising, dusting, scattering, brushing or pouring, and likewise the type of composition, are selected to suit the objectives to be achieved and the given conditions.

The formulations, that is to say, the compositions or preparations containing the active ingredient of the formula I, or a combination of active ingredient of the formula I and agricultural chemicals to be antagonised, and optionally a solid or liquid additive, are produced in a known manner, for example by the intimate mixing and/or grinding of the active ingredients with extenders, such as with solvents, solid carriers and optionally surface active compounds (tensides).

Suitable solvents are: aromatic hydrocarbons, preferably the fractions C₈ to C₁₂, such as xylene mixtures or substituted naphthalenes, phthalic esters, such as dibutyl- or dioctylphthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols, as well as ethers and esters thereof, such as ethanol, ethylene glycol, ethylene glycol monomethyl or -ethyl ethers, ketones such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as optionally epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used, for example for dusts and dispersible powders, are as a rule natural mineral fillers, such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties, it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, ground brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. There can also be used a great number or pre-granulated materials of inorganic or organic nature, such as in particular dolomite or ground plant residues.

Suitable surface-active compounds are, depending on the nature of the active ingredient of the formula I to be formulated, and optionally also of the agricultural chemical to be antagonised, nonionic, cationic and/or anionic tensides having good emulsifying, dispersing and wetting properties. By `tensides` are also meant mixtures of tensides.

Suitable anionic tensides are both so-called water-soluble soaps as well as water-soluble, synthetic, surface-active compounds.

Soaps which are applicable are the alkali metal, alkaline-earth metal or optionally substituted ammonium salts of higher fatty acids (C₁₀ -C₂₂), for example the Na or K salts of oleic or stearic acid, or of natural fatty acid mixtures, which can be obtained for example from coconut oil or tallow oil. Also to be mentioned are the fatty acid-methyl-laurine salts.

So-called sythetic tensides are however more frequently used, particularly fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates. The fatty sulfonates or sulfates are as a rule in the form of alkali metal, alkaline-earth metal or optionally substituted ammonium salts, and contain an alkyl group having 8 to 22 C atoms, `alkyl` including also the alkyl moiety of acyl groups, for example the Na or Ca salt of ligninsulfonic acid, of dodecylsulfuric acid ester or of a fatty alcohol sulfate mixture produced from natural fatty acids. Included among these are also the salts of sulfuric acid esters and sulfonic acids of fatty alcohol ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid group having 8-22 C atoms. Alkylarylsulfonates are for example the Na, Ca or triethanolamide salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid-formaldehyde condensation product. Also suitable are corresponding phosphates, for example salts of the phosphoric ester of a p-nonylphenol-(4-14)-ethylene oxide adduct, or phospholipides.

Suitable nonionic tensides are in particular polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Further suitable nonionic tensides are the water-soluble polyethylene oxide adducts, which contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups, with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Examples of nonionic tensides which may be mentioned are: nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Suitable also are fatty acid esters of polyoxyethylenesorbitan, such as polyoxyethylenesorbitan-trioleate.

In the case of the cationic tensides, they are in particular quaternary ammonium salts which contain as N-substituents at least one alkyl group having 8 to 22 C atoms and, as further substituents, lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl groups. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, for example stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The tensides customarily used in formulation practice are described, inter alia, in the following publications:

"McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ringwood, N.J., 1980, and

Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1980.

The agrochemical preparations contain as a rule 0.1 to 99%, particularly 0.1 to 95%, of active ingredient of the formula I, 99.9 to 1%, especially 99.8 to 5%, of a solid or liquid additive, and 0 to 25%, in particular 0.1 to 25%, of a tenside. Whereas commercial products are preferably in the form of concentrated compositions, the compositions employed by the end-user are as a rule diluted.

The compositions can also contain further additives, such as stabilisers, antifoam agents, viscosity regulators, binders and adhesives, as well as fertilisers or other active substances for obtaining special effects.

For the use of compounds of the formula I, or of compositions containing them, for the protection of cultivated plants against the harmful effects of aggressive agricultural chemicals, various methods and techniques are applicable, such as those described in the following.

(i) Seed dressing

(a) Dressing of the seeds with an active ingredient, formulated as a wettable powder, by shaking in a vessel until there is a uniform distribution over the surface of the seeds (dry dressing). The amount of active ingredient of the formula I used for this purpose is about 10 to 500 g (40 g to 2 kg of wettable powder) per 100 kg of seed.

(b) Dressing of the seeds with an emulsion concentrate of the active ingredient of the formula I according to method (a) (wet dressing).

(c) Dressing by immersion of the seed in a liquor containing 50-3200 ppm of active ingredient of the formula I for 1 to 72 hours, and optionally subsequent drying of the seed (immersion dressing).

The dressing of the seed or the treatment of the germinated young seedlings is, in accordance with nature, the preferred method of application, because the treatment with the active ingredient is directed completely at the target growth. There are used as a rule 10 g to 500 g, preferably 50 to 250 g of active substance (AS) per 100 kg of seed, whereby, depending on the method of treatment, which may render possible also the addition of other active substances or micronutrients, the stated limiting concentrations can be varied upwards or downwards (repeat dressing).

(ii) Application as tank mixture

A liquid preparation of a mixture of antidote and herbicide (quantitative ratio between 10:1 and 1:10) is used, the applied amount of herbicide being 0.1 to 10 kg per hectare. This tank mixture is preferably applied before or immediately after sowing, or it is worked into the unsown soil to a depth of 5 to 10 cm.

(iii) Application into the seed furrow

The antidote is introduced, as an emulsion concentrate, wettable powder or granulate, into the open sown seed furrow, and, after the covering of the seed furrow in the normal manner, the herbicide is applied before emergence of the plants.

(iv) Controlled release of active ingredient

The active ingredient is absorbed, in solution, onto mineral granular carriers or polymerised granulates (urea/formaldehyde), and the material is allowed to dry. A coating can if required be applied (coated granules), which enables the active ingredients to be released in controlled amounts over a certain period of time.

Compounds of the formula I in which at the same time R₁, R₂, R₄, R₅ and R₆ are hydrogen, R₃ is hydrogen or chlorine, A is one of the groups --CH₂ -- or --CH(CH₃)-- and Z is cyano or the group ##STR11## are known from Areschka et al., Eur. J. Med. Chem.--Chimica Therapeutica, September-October 1975, 10, (5), 463-469. Some of these compounds have anti-aggressive properties.

The remaining compounds of the formula I are novel and are subject matter of the present invention. They correspond to the formula Ia ##STR12## wherein R₁ ', R₂ ' and R₃ ' independently of one another are each hydrogen, halogen,, C₁ -C₃ -alkyl, C₁ -C₃ -alkoxy, nitro or cyano,

R₄ ', R₅ ' and R₆ ' independently of one another are each hydrogen, halogen or C₁ -C₃ -alkyl,

A' is any one of th groups --C₂ --, --CH₂ --CH₂ -- or --CH(CH₃)--, and

Z' is cyano or amidoxime which can be acylated on the oxygen atom,

including acid addition salts and metal complexes thereof, with the proviso that Z' is not cyano or amidoxime when simultaneously R₁ ', R₂ ', R₄ ', R₅ ' and R₆ ' are hydrogen, R₃ ' is hydrogen or chlorine, and A' is --CH₂ -- or --CH(CH₃)--.

Preferred compounds of the formula Ia are those wherein R₁ ', R₂ ' and R₃ ' independently of one another are each hydrogen, halogen, C₁ -C₃ -alkyl, C₁ -C₃ -alkoxy, nitro or cyano,

R₄ ', R₅ ' and R₆ ' independently of one another are each hydrogen, halogen or C₁ -C₃ -alkyl,

A' is any one of the groups --C₂ --, --CH₂ --CH₂ -- or --CH(CH₃)--, and

Z' is cyano or either one of the groups ##STR13## in which E is --R₇, --OR₈, --SR₉ or --NR₁₀ R₁₁, wherein R₇ is C₁ -C₇ -alkyl which is unsubstituted or substituted by halogen or C₁ -C₄ -alkoxy, or R₇ is C₃ -C₆ -cycloalkyl, C₂ -C₄ -alkenyl, phenyl which is unsubstituted or substituted by halogen, nitro or C₁ -C₃ -alkyl, or it is benzyl which is unsubstituted or substituted by halogen, nitro or C₁ -C₃ -alkyl, or R₇ is a 5- or 6-membered heterocyclic ring which contains one or two hetero atoms from the group N, O and S, and which is unsubstituted or substituted by halogen; and R₈, R₉ and R₁₀ independently of one another are each C₁ -C₈ -alkyl which is unsubstituted or substituted by halogen, or each are C₂ -C₄ -alkenyl, C₃ -C₆ -alkynyl, phenyl which is unsubstituted or substituted by halogen, C₁ -C₃ -alkyl, C₁ -C₃ -alkoxy, trifluoromethyl or nitro, or they are each benzyl which is unsubstituted or substituted by halogen or nitro, R₁₁ is hydrogen, C₁ -C₈ -alkyl or C₁ -C₃ -alkoxy, or R₁₀ and R₁₁ together with the nitrogen atom to which they are bound form a 5- or 6-membered heterocyclic radical which can also contain a further hetero atom from the group N, O and S;

including acid addition salts and metal complexes thereof, with the proviso that Z' is not cyano or amidoxime when simultaneously R₁ ', R₂ ', R₄ ', R₅ ' and R₆ ' are hydrogen, R₃ ' is hydrogen or chlorine, and A' is --CH₂ -- or --CH(CH₃)--.

Preferred compounds of this group are those wherein R₁ ' is hydrogen, chlorine, bromine, iodine or nitro, R₂ ' is hydrogen, R₃ ' is hydrogen, fluorine, chlorine, bromine, iodine, C₁ -C₃ -alkyl or nitro, R₄ ' is hydrogen, bromine or methyl, R₅ ' is hydrogen, R₆ ' is hydrogen or methyl, A' is --CH₂ --, --CH₂ --CH₂ -- or --CH(CH₃)--, and Z' is cyano, ##STR14## in which E is --R₇, --OR₈, --SR₉ or --NR₁₀ R₁₁, wherein R₇ is C₁ -C₇ -alkyl, C₁ -C₃ -alkyl which is substituted by 1 to 3 chlorine or bromine atoms, or R₇ is C₁ -C₄ -alkoxymethyl, C₃ -C₆ -cycloalkyl, C₂ -C₃ -alkenyl, phenyl which is unsubstituted or substituted by one or two substituents from the group chlorine, nitro and methyl, or it is benzyl which is unsubstituted or monosubstituted by chlorine or nitro, or R₇ is a thiophene, furan, tetrahydrofuran or pyrimidine ring each of which is unsubstituted or mono- or disubstituted by chlorine or bromine, R₈ is C₁ -C₄ -alkyl, ethyl monosubstituted by chlorine or bromine, or it is C₂ -C₃ -alkenyl, propynyl, phenyl which is unsubstituted or monosubstituted by nitro, or it is benzyl which is unsubstituted or monosubstituted by nitro, R₉ is C₁ -C₇ -alkyl, R₁₀ is C₁ -C₄ -alkyl, chloroethyl, or phenyl which is unsubstituted or substituted by one or two substituents from the group chlorine, methoxy and trifluoromethyl, and R₁₁ is hydrogen, methyl or methoxy, or R₁₀ and R₁₁ jointly with the nitrogen atom to which they are bound form a piperidine or morpholine ring, with the proviso that Z' is not cyano or amidoxime when simultaneously R₁ ', R₂ ', R₄ ', R₅ ' and R₆ ' are hydrogen, R₃ ' is hydrogen or chlorine, and A' is --CH₂ -- or --CH(CH₃)--.

Compounds of this group to be emphasised are in particular those in which R₁ ' is hydrogen, chlorine, bromine or iodine, R₂ ' is hydrogen, R₃ ' is hydrogen, chlorine or nitro, R₄ ' and R₅ ' are hydrogen, R₆ ' is hydrogen or methyl, A' is --CH₂ --, --CH₂ --CH₂ -- or --CH(CH₃)-- and Z' is cyano, ##STR15## in which E is --R₇, --OR₈, --SR₉ or --NR₁₀ R₁₁, wherein R₇ is methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, chloromethyl, bromomethyl, 2-chloroethyl, 3-chloro-n-propyl, 1,2-dichloroethyl, methoxymethyl, n-propoxymethyl, sec-butoxymethyl, cyclopropyl, vinyl, 1-propenyl, isopropenyl, phenyl, 2-chlorophenyl, 4-chlorophenyl, benzyl, 2-thienyl, 2-furyl, 5-bromo-2-furyl, 2-tetrahydrofuryl or 2,4-dichloropyrimidin-5-yl, R₈ is methyl, ethyl, n-propyl, n-butyl, 2-bromoethyl, allyl, phenyl or benzyl, R₉ is ethyl, isopropyl or n-pentyl, R₁₀ is methyl, ethyl, isopropyl, n-butyl, phenyl, 3-trifluoromethylphenyl, 4-chlorophenyl or 2,5-dichlorophenyl, and R₁₁ is hydrogen or methoxy, with the proviso that Z' is not cyano or amidoxime when simultaneously R₁ ', R₂ ', R₄ ', R₅ ' and R₆ ' are hydrogen, R₃ ' is hydrogen or chlorine, and A' is --CH₂ -- or --CH(CH₃)--.

More especially preferred are compounds of the formula Ia in which R₁ ' is hydrogen, chlorine, bromine or iodine, R₂ ' is hydrogen, R₃ ' is hydrogen or chlorine, R₄ ' and R₅ ' are hydrogen, R₆ ' is hydrogen or methyl, A' is --CH₂ --, and Z' is cyano, ##STR16## in which E is --R₇, --OR₈ or --NR₁₀ R₁₁, wherein R₇ is chloromethyl, R₈ is methyl, R₁₀ is isopropyl, and R₁₁ is hydrogen, with the proviso that Z' is not cyano or amidoxime when simultaneously R₁ ', R₂ ', R₄ ', R₅ ' and R₆ ' are hydrogen, R₃ ' is hydrogen or chlorine, and A' is --CH₂ --.

The following compounds are to be especially emphasised:

2-methyl-8-(cyanomethoxy)-quinoline,

2-(2-methyl-8-quinolinoxy)-acetamide oxime,

O-(isopropylaminocarbonyl)-2-(8-quinolinoxy)-acetamide oxime,

O-(chloromethylcarbonyl)-2-(8-quinolinoxy)-acetamide oxime,

2-(5-chloro-7-bromo-8-quinolinoxy)-acetamide oxime,

5-chloro-7-bromo-8-(cyanomethoxy)-quinoline,

O-(methoxycarbonyl)-2-(8-quinolinoxy)-acetamide oxime,

2-(5-chloro-7-iodo-8-quinolinoxy)-acetamide oxime,

O-(isopropylaminocarbonyl)-2-(5-chloro-7-bromo-8-quinolinoxy)-acetamide oxime,

2-(2-methyl-5,7-dichloro-8-quinolinoxy)-acetamide oxime,

5,7-dichloro-8-(cyanomethoxy)-quinoline,

O-(isopropylaminocarbonyl)-2-(5-chloro-7-iodo-8-quinolinoxy)-acetamide oxime,

2-methyl-5,7-dichloro-8-(cyanomethoxy)-quinoline,

O-(isopropylaminocarbonyl)-2-(2-methyl-5,7-dichloro-8-quinolinoxy)-acetamide oxime,

and in particular

5-chloro-7-iodo-8-(cyanomethoxy)-quinoline.

Compounds of the formula Ia are produced by the following procedures:

(a) compounds of the formula Ia in which R₁ ', R₂ ', R₃ ', R₄ ', R₅ ' and R₆ ' have the meanings defined for the formula Ia, A' is the group --CH₂ --CH₂ --, and Z' is cyano, are produced by reacting a compound of the formula II ##STR17## wherein R₁ ', R₂ ', R₃ ', R₄ ', R₅ ' and R₆ ' have the meanings given in the foregoing, with a compound of the formula III

    CH.sub.2 ═CH--CN                                       (III); or

(b) compounds of the formula Ia in which R₁ ', R₂ ', R₃ ', R₄ ', R₅ ' and R₆ ' have the meanings defined under the formula Ia, A' is a group --CH₂ -- or --CH(CH₃)--, and Z' is cyano, are produced by reacting a compound of the formula II ##STR18## wherein R₁ ', R₂ ', R₃ ', R₄ ', R₅ ' and R₆ ' have the meanings given for the formula II,

(i) with a compound of the formula IV

    Hal--A'--CN                                                (IV),

wherein Hal is a halogen atom, and A' has the meaning defined in the foregoing, or

(ii) with a compound of the formula V ##STR19## wherein A' has the meaning defined in the foregoing, or (iii) with a compound of the formula VI

    Hal--A'--COOR.sub.12                                       (VI),

wherein Hal is a halogen atom, R₁₂ is an alkyl group having 1 to 6 carbon atoms, and A' has the meaning defined in the foregoing; and converting the resulting ester of the formula VII ##STR20## wherein R₁ ', R₂ ', R₃ ', R₄ ', R₅ ', R₆ ', A' and R₁₂ have the meanings defined in the foregoing, with ammonia into the corresponding amide of the formula VIII ##STR21## wherein R₁ ', R₂ ', R₃ ', R₄ ', R₅ ', R₆ ' and A' have the meanings defined above, and then dehydrating the product obtained; and/or

(c) compounds of the formula Ia in which R₁ ', R₂ ', R₃ ', R₄ ', R₅ ' R₆ ' and A' have the meanings defined for the formula Ia, and Z' is amidoxime which can be acylated on the oxygen atom, are produced by reacting a compound of the formula Ia wherein R₁ ', R₂ ', R₃ ', R₄ ', R₅ ', R₆ ' and A' have the meanings defined for the formula Ia, and Z' is cyano, with hydroxylamine or with an acid salt of hydroxylamine; and/or

(d) compounds of the formula Ia in which R₁ ', R₂ ', R₃ ', R₄ ', R₅ ', R₆ ' and A' have the meanings defined for the formula Ia, and Z' is acylated amidoxime, are produced by acylating a compound of the formula Ia wherein R₁ ', R₂ ', R₃ ', R₄ ', R₅ ', R₆ ' and A' have the meanings given for the formula Ia, and Z' is amidoxime.

Thus, for example, compounds of the formula Ia in which R₁ ', R₂ ', R₃ ', R₄ ', R₅ ', R₆ ' and A' have the meanings defined for the formula Ia, and Z' is acylated amidoxime of the formula ##STR22## wherein E is --R₇, OR₈, --SR₉ or --NR₁₀ R₁₁, in which R₇ is C₁ -C₇ -alkyl which is unsubstituted or substituted by halogen or C₁ -C₄ -alkoxy, or R₇ is C₃ -C₆ -cycloalkyl, C₂ -C₄ -alkenyl, phenyl which is unsubstituted or substituted by halogen, nitro or C₁ -C₃ -alkyl, or it is benzyl unsubstituted or substituted by halogen, nitro or C₁ -C₃ -alkyl, or R₇ is a 5- or 6-membered heterocyclic ring which contains one or two hetero atoms from the group N, O and S, and which is unsubstituted or substituted by halogen, R₈, R₉ and R₁₀ independently of one another are each C₁ -C₈ -alkyl which is unsubstituted or substituted by halogen, or they are each C₂ -C₄ -alkenyl, C₃ -C₆ -alkynyl, phenyl which is unsubstituted or substituted by halogen, C₁ -C₃ -alkyl, C₁ -C₃ -alkyl, C₁ -C₃ -alkoxy, trifluoromethyl or nitro, or are each benzyl which is unsubstituted or substituted by halogen or nitro, and R₁₁ is hydrogen, C₁ -C₈ -alkyl or C₁ -C₃ -alkoxy, or R₁₀ and R₁₁ together with the nitrogen atom to which they are bound form a 5- to 6-membered heterocyclic radical which can also contain a further hetero atom from the group N, O and S, can be produced by reacting a compound of the formula Ia, wherein R₁ ', R₂ ', R₃ ', R₄ ', R₅ ', R₆ ' and A' have the meanings defined for the formula Ia, and Z' is amidoxime, with a compound of the formula IX ##STR23## in which X is a halogen atom and Y is --R₇, --OR₈, --SR₉ or --NR₁₀ R₁₁, wherein R₇, R₈, R₉, R₁₀ and R₁₁ have the meanings defined in the foregoing, or X and Y together are the imino group ═N--R₁₀.

The reaction (a) of compounds of the formula II with compounds of the formula III is preferably performed in the presence of a basic catalyst. Particularly suitable as catalysts are metal alcholates, especially alkali metal and alkaline-earth metal alcoholates, or hydroxides, for example sodium hydroxide.

The reaction (b/i) of compounds of the formula II with compounds of the formula IV is carried out preferably in methyl ethyl ketone in the presence of potassium carbonate, or in dimethylformamide in the presence of sodium hydride, whilst the reaction (b/ii) of compounds of the formula II with compounds of the formula V is performed most advantageously in a two-phase system, the one phase being water and the other phase being a liquid immiscible with water, such as toluene or methylene chloride. The catalyst used in these reactions is a phase-transfer catalyst, for example benzyltriethylammonium chloride.

In the compounds of the formula IV, Hal is chlorine, bromine, fluorine or iodine. Chlorine and bromine are preferred, the catalyst employed being advantageously potassium iodide.

In the compounds of the formula VI, Hal is chlorine, bromine, iodine or fluorine.

The dehydration (b/iii) of amides of the formula VIII to the corresponding nitriles can be performed in a known manner, for example with phosphorus pentoxide or with phosphorus oxychloride.

Suitable for the reaction (c) of nitriles of the formula Ia with hydroxylamine or with acid salts of hydroxylamine are in particular salts of hydroxylamine with inorganic acids, especially hydroxylamine hydrochloride or hydroxylamine sulfate, the reaction with acid salts being advantageously performed in the presence of a base, for example hydroxides of alkali metals or alkaline-earth metals, such as sodium hydroxide, or tertiary organic bases, for example tertiary amines, such as pyridine or trialkylamine.

In the formula IX, X is chlorine, bromine, fluorine or iodine.

The quinolines and quinaldines to be used as starting products are known, or they can be produced by processes analogous to known processes.

The known compounds of the formula I which are not embraced by the formula Ia can be produced by the methods described for compounds of the formula Ia.

The Examples which follow serve to further illustrate the invention.

PRODUCTION EXAMPLES FOR ACTIVE INGREDIENTS Example 1 2-Methyl-5,7-dichloro-8-(cyanomethoxy)-quinoline (Compound No. 18)

10.7 g of 5,7-dichloro-8-hydroxyquinaldine are dissolved at elevated temperature in 150 ml of 2-butanone; 10.4 g of potassium carbonate are then added portionwise, and the mixture is refluxed for one hour. After the addition of 1 g of potassium iodide, there are added dropwise, with stirring and refluxing, 7.1 g of chloroacetonitrile in 30 ml of 2-butanone, and the mixture is subsequently heated for 3 hours at an internal temperature of 75° C. To the resulting reaction mixture, after cooling to room temperature, is added 1 liter of water, and the whole is filtered; the residue is washed with water, dried, and recrystallised from chloroform/petroleum ether (40°-60° C.) to thus obtain 2-methyl-5,7-dichloro-8-(cyanomethoxy)-quinoline, m.p. 157°-158° C.

Example 2 2-(8-Quinolinoxy)-acetamide oxime (Compound No. 2)

A solution of 6.4 g of hydroxylamine hydrochloride in 10 ml of water and 6.4 g of potassium carbonate in 10 ml of water is added dropwise at room temperature, within 15 minutes, to 15.8 g of 8-(cyanomethoxy)-quinoline in 100 ml of ethanol, in the course of which the reaction mixture warms up to 30° C. After 3 hours' stirring at room temperature, the reaction mixture is diluted with 250 ml of water; it is subsequently filtered, and the residue is washed with water and dried. There is thus obtained 2-(8-quinolinoxy)-acetamide oxime in the form of light-brown powder, m.p. 201°-204° C. (decomposition).

Example 3 O-(Isopropylaminocarbonyl)-2-(5-chloro-7-bromo-8-quinolinoxy)-acetamide oxime (Compound No. 14)

3.3 g of isopropylisocyanate and 0.1 g of 1,4-diazabicyclo[2,,2,2]octane are added at 65° C. with stirring, within 15 minutes, to 8.6 g of 2-(5-chloro-7-bromo-8-quinolinoxy)acetamide oxime in 100 ml of acetonitrile, and the mixture is subsequently heated at 60° C. for two hours. After cooling to room temperature, the reaction mixture is filtered, and the residue is washed with a small amount of acetonitrile and subsequently dried. O-(Isopropylaminocarbonyl)-2-(5-chloro-7-bromo-8-quinolinoxy)-acetamide oxime is thus obtained in the for of white crystals, m.p. 162°-165° C.

It is possible to produce, by methods analogous to those described in the foregoing, also the following compounds of the formulae I and Ia, which are listed in Table 1 together with the compounds of the above Examples.

                                      TABLE 1                                      __________________________________________________________________________      ##STR24##                                                                     No. R.sub.1                                                                           R.sub.2                                                                          R.sub.3                                                                            R.sub.4                                                                           R.sub.5                                                                          R.sub.6                                                                           A    Z                Physical data                       __________________________________________________________________________                                                m.p.                                1   H  H H   H  H H  CH.sub.2                                                                            CN               118-119° C.                  2   H  H H   H  H H  CH.sub.2                                                                             ##STR25##       201-204° C. (decomp.)        3   H  H H   H  H CH.sub.3                                                                          CH.sub.2                                                                            CN               114-116° C.                  4   H  H H   H  H CH.sub.3                                                                          CH.sub.2                                                                             ##STR26##       209-210° C. (decomp.)        5   H  H Cl  H  H H  CH.sub.2                                                                             ##STR27##       203-205° C. (decomp.)        6   H  H H   H  H H  CH.sub.2                                                                             ##STR28##       136-138° C.                  7   H  H Cl  H  H H  CH.sub.2                                                                            CN               159-160° C.                  8   H  H H   H  H H  CH.sub.2                                                                             ##STR29##       129-130° C.                  9   Br H Cl  H  H H  CH.sub.2                                                                             ##STR30##       197-198° C. (decomp.)        10  Br H Cl  H  H H  CH.sub.2                                                                            CN               150-151° C.                  11  H  H H   H  H H  CH.sub.2                                                                             ##STR31##       143-145° C.                  12  J  H Cl  H  H H  CH.sub.2                                                                             ##STR32##       195-196° C. (decomp.)        13  J  H Cl  H  H H  CH.sub.2                                                                            CN               141-143° C.                  14  Br H Cl  H  H H  CH.sub.2                                                                             ##STR33##       162-165° C.                  15  Cl H Cl  H  H CH.sub.3                                                                          CH.sub.2                                                                             ##STR34##       205-207° C. (decomp.)        16  Cl H Cl  H  H H  CH.sub.2                                                                            CN               150-152° C.                  17  J  H Cl  H  H H  CH.sub.2                                                                             ##STR35##       163-167° C.                  18  Cl H Cl  H  H CH.sub.3                                                                          CH.sub.2                                                                            CN               157-158° C.                  19  Cl H Cl  H  H CH.sub.3                                                                          CH.sub.2                                                                             ##STR36##       149-152° C.                  20  H  H H   H  H H                                                                                  ##STR37##                                                                          CN               108-112° C.                  21  H  H H   CH.sub.3                                                                          H H  CH.sub.2                                                                            CN                                                   22  H  H H   H  H H                                                                                  ##STR38##                                                                          CN               121-124° C.                  23  H  H CH.sub.3                                                                           H  H H  CH.sub.2                                                                            CN                                                   24  H  H H   H  H H                                                                                  ##STR39##                                                                           ##STR40##       186-189° C.                  25  H  H H   H  H CH.sub.3                                                                           ##STR41##                                                                          CN                                                   26  H  H C.sub.2 H.sub.5                                                                    H  H H  CH.sub.2                                                                            CN                                                   27  H  H Br  H  H H  CH.sub.2                                                                             ##STR42##                                           28  H  H H   H  H CH.sub.3                                                                           ##STR43##                                                                          CN                                                   29  H  H H   Br H H  CH.sub.2                                                                            CN                                                   30  H  H H   H  H CH.sub.3                                                                           ##STR44##                                                                           ##STR45##                                           31  H  H Cl  H  H H                                                                                  ##STR46##                                                                          CN               143-145° C.                  32  H  H J   H  H H  CH.sub.2                                                                             ##STR47##                                           33  H  H Br  H  H H                                                                                  ##STR48##                                                                          CN                                                   34  H  H Br  H  H CH.sub.3                                                                          CH.sub.2                                                                             ##STR49##                                           35  H  H H   H  H H                                                                                  ##STR50##                                                                           ##STR51##       191-194° C. (decomp.)        36  H  H F   H  H H  CH.sub.2                                                                            CN                                                   37  H  H Cl  H  H CH.sub.3                                                                          CH.sub.2                                                                             ##STR52##                                           38  H  H Br  H  H CH.sub.3                                                                           ##STR53##                                                                          CN                                                   39  H  H H   H  H CH.sub.3                                                                           ##STR54##                                                                           ##STR55##                                           40  H  H Br  H  H H  CH.sub.2                                                                            CN                                                   41  Cl H Br  H  H H  CH.sub.2                                                                             ##STR56##                                           42  H  H J   H  H H  CH.sub.2                                                                            CN                                                   43  H  H Cl  H  H CH.sub.3                                                                           ##STR57##                                                                          CN                                                   44  H  H Br  H  H CH.sub.3                                                                          CH.sub.2                                                                            CN                                                   45  Cl H Br  H  H H                                                                                  ##STR58##                                                                          CN                                                   46  H  H Cl  H  H CH.sub.3                                                                          CH.sub.2                                                                            CN                                                   47  H  H Cl  H  H H                                                                                  ##STR59##                                                                           ##STR60##       186-189° C. (decomp.)        48  Cl H Br  H  H CH.sub.3                                                                          CH.sub.2                                                                             ##STR61##                                           49  H  H J   H  H CH.sub.3                                                                          CH.sub.2                                                                            CN                                                   50  H  H Br  H  H H                                                                                  ##STR62##                                                                           ##STR63##                                           51  Cl H Br  H  H H  CH.sub.2                                                                            CN                                                   52  Br H Cl  H  H H                                                                                  ##STR64##                                                                          CN                                                   53  Br H Cl  H  H CH.sub.3                                                                          CH.sub.2                                                                             ##STR65##                                           54  Cl H Br  H  H CH.sub.3                                                                          CH.sub.2                                                                            CN                                                   55  H  H Br  H  H CH.sub.3                                                                           ##STR66##                                                                           ##STR67##                                           56  Br H Cl  H  H CH.sub.3                                                                          CH.sub.2                                                                            CN                                                   57  J  H Cl  H  H H                                                                                  ##STR68##                                                                          CN                                                   58  J  H Br  H  H H  CH.sub.2                                                                            CN                                                   59  H  H Cl  H  H CH.sub.3                                                                           ##STR69##                                                                           ##STR70##                                           60  Br H J   H  H H  CH.sub.2                                                                            CN                                                   61  H  H NO.sub.2                                                                           H  H H                                                                                  ##STR71##                                                                          CN               154-156° C.                  62  Br H NO.sub.2                                                                           H  H H  CH.sub.2                                                                            CN                                                   63  J  H Cl  H  H CH.sub.3                                                                          CH.sub.2                                                                             ##STR72##                                           64  Cl H J   H  H H  CH.sub.2                                                                            CN                                                   65  Cl H NO.sub.2                                                                           H  H H  CH.sub.2                                                                             ##STR73##       214-216° C. (decomp.)        66  J  H Cl  H  H CH.sub.3                                                                          CH.sub.2                                                                            CN                                                   67  Br H Br  H  H H  CH.sub.2                                                                             ##STR74##                                           68  Cl H H   H  H CH.sub.3                                                                          CH.sub.2                                                                            CN                                                   69  Cl H Br  H  H H                                                                                  ##STR75##                                                                           ##STR76##                                           70  Cl H NO.sub.2                                                                           H  H H  CH.sub.2                                                                            CN               166-169° C.                  71  Cl H Cl  H  H H  CH.sub.2                                                                             ##STR77##                                           72  Cl H C.sub.3 H.sub.7 n                                                                  H  H H  CH.sub.2                                                                            CN                                                   73  Br H Br  H  H H  CH.sub.2                                                                            CN                                                   74  Br H Br  H  H CH.sub.3                                                                          CH.sub.2                                                                            CN                                                   75  Br H Cl  H  H H                                                                                  ##STR78##                                                                           ##STR79##                                           76  J  H J   H  H H  CH.sub.2                                                                             ##STR80##                                           77  H  H H   H  H H  CH.sub.2                                                                             ##STR81##       165-166° C.                  78  J  H J   H  H H  CH.sub.2                                                                            CN                                                   79  H  H H   H  H H  CH.sub.2                                                                             ##STR82##       139-141° C.                  80  J  H J   H  H CH.sub.3                                                                          CH.sub.2                                                                            CN                                                   81  H  H H   H  H H  CH.sub.2                                                                             ##STR83##                                           82  NO.sub.2                                                                          H NO.sub.2                                                                           H  H H  CH.sub.2                                                                            CN                                                   83  NO.sub.2                                                                          H NO.sub.2                                                                           H  H CH.sub.3                                                                          CH.sub.2                                                                             ##STR84##                                           84  J  H F   H  H H  CH.sub.2                                                                            CN                                                   85  H  H Cl  H  H H  CH.sub.2                                                                             ##STR85##       141-143° C.                  86  J  H NO.sub.2                                                                           H  H CH.sub.3                                                                          CH.sub.2                                                                            CN                                                   87  H  H Cl  H  H H  CH.sub.2                                                                             ##STR86##                                           88  NO.sub.2                                                                          H NO.sub.2                                                                           H  H CH.sub.3                                                                          CH.sub.2                                                                            CN                                                   89  H  H Cl  H  H H  CH.sub.2                                                                             ##STR87##                                           90  H  H NO.sub.2                                                                           H  H H  CH.sub.2                                                                            CN               162-164° C.                  91  J  H Cl  H  H H                                                                                  ##STR88##                                                                           ##STR89##                                           92  H  H NO.sub.2                                                                           H  H H  CH.sub.2                                                                             ##STR90##       212-215° C. (decomp.)        93  H  H NO.sub.2                                                                           H  H CH.sub.3                                                                          CH.sub.2                                                                            CN                                                   94  H  H Cl  H  H H  CH.sub.2                                                                             ##STR91##       148-149° C.                  95  H  H H   H  H CH.sub.3                                                                          CH.sub.2                                                                             ##STR92##                                           96  H  H NO.sub.2                                                                           H  H H                                                                                  ##STR93##                                                                           ##STR94##                                           97  H  H H   H  H CH.sub.3                                                                          CH.sub.2                                                                             ##STR95##                                           98  H  H Cl  H  H H  CH.sub.2                                                                             ##STR96##       139-140° C.                  99  H  H H   H  H H  CH.sub.2                                                                             ##STR97##       111-114° C.                  100 H  H H   H  H H  CH.sub.2                                                                             ##STR98##                                           101 H  H H   H  H H  CH.sub.2                                                                             ##STR99##       158-162° C.                  102 H  H H   H  H H  CH.sub.2                                                                             ##STR100##      123-125° C.                  103 H  H H   H  H H  CH.sub.2                                                                             ##STR101##      138-139° C.                  104 H  H H   H  H H  CH.sub.2                                                                             ##STR102##      120-122° C.                  105 H  H Cl  H  H H  CH.sub.2                                                                             ##STR103##      157-158° C. (decomp.)        106 H  H H   H  H H  CH.sub.2                                                                             ##STR104##                                          107 H  H Cl  H  H H  CH.sub.2                                                                             ##STR105##                                          108 H  H H   H  H H  CH.sub.2                                                                             ##STR106##      144-146° C.                  109 H  H Cl  H  H H  CH.sub.2                                                                             ##STR107##                                          110 H  H H   H  H H  CH.sub.2                                                                             ##STR108##      112-114° C.                  111 H  H Cl  H  H H  CH.sub.2                                                                             ##STR109##      173-174° C.                  112 H  H H   H  H H  CH.sub.2                                                                             ##STR110##                                          113 H  H Cl  H  H H  CH.sub.2                                                                             ##STR111##                                          114 H  H H   H  H H  CH.sub.2                                                                             ##STR112##      155-156° C.                  115 H  H H   H  H H  CH.sub.2                                                                             ##STR113##                                          116 H  H H   H  H H  CH.sub.2                                                                             ##STR114##        107-110,5° C.              117 H  H H   H  H H  CH.sub.2                                                                             ##STR115##      124-126° C.                  118 H  H H   H  H H  CH.sub.2                                                                             ##STR116##      131-132° C.                  119 H  H Cl  H  H H  CH.sub.2                                                                             ##STR117##                                          120 H  H H   H  H H  CH.sub.2                                                                             ##STR118##                                          121 H  H H   H  H H  CH.sub.2                                                                             ##STR119##                                          122 H  H H   H  H H  CH.sub.2                                                                             ##STR120##      84-86° C.                    123 H  H H   H  H H  CH.sub.2                                                                             ##STR121##      168-169° C.                  124 H  H H   H  H H  CH.sub.2                                                                             ##STR122##      100-103° C.                  125 H  H H   H  H H  CH.sub.2                                                                             ##STR123##                                          126 H  H Cl  H  H H  CH.sub.2                                                                             ##STR124##                                          127 H  H Cl  H  H H  CH.sub.2                                                                             ##STR125##      156-157° C. (decomp.)        128 H  H H   H  H H  CH.sub.2                                                                             ##STR126##      82-85° C.                    129 H  H H   H  H H  CH.sub.2                                                                             ##STR127##      144-147° C.                  130 H  H H   H  H H  CH.sub.2                                                                             ##STR128##                                          131 H  H H   H  H H  CH.sub.2                                                                             ##STR129##      128-130° C.                  132 H  H H   H  H H  CH.sub.2                                                                             ##STR130##                                          133 H  H H   H  H H  CH.sub.2                                                                             ##STR131##                                          134 H  H H   H  H H  CH.sub.2                                                                             ##STR132##      90-92° C.                    135 H  H Cl  H  H H  CH.sub.2                                                                             ##STR133##                                          136 H  H Cl  H  H H  CH.sub.2                                                                             ##STR134##                                          137 H  H H   H  H H  CH.sub.2                                                                             ##STR135##      132-134° C.                  138 H  H H   H  H H  CH.sub.2                                                                             ##STR136##                                          139 H  H H   H  H H  CH.sub.2                                                                             ##STR137##      138-140° C.                  140 H  H H   H  H H  CH.sub.2                                                                             ##STR138##      129-131° C.                  141 H  H H   H  H H  CH.sub.2                                                                             ##STR139##                                          142 H  H H   H  H H  CH.sub.2                                                                             ##STR140##      121-123° C.                  143 H  H H   H  H H  CH.sub. 2                                                                            ##STR141##      123-125° C.                  144 H  H Cl  H  H H  CH.sub.2                                                                             ##STR142##                                          145 H  H H   H  H H  CH.sub.2                                                                             ##STR143##                                          146 H  H H   H  H H  CH.sub.2                                                                             ##STR144##                                          147 H  H H   H  H H  CH.sub.2                                                                             ##STR145##      127-128° C. (decomp.)        148 H  H H   H  H H  CH.sub.2                                                                             ##STR146##                                          149 H  H Cl  H  H H  CH.sub.2                                                                             ##STR147##      173-175° C.                  150 H  H H   H  H H  CH.sub.2                                                                             ##STR148##                                          151 H  H H   H  H H  CH.sub.2                                                                             ##STR149##      135-137° C.                  152 H  H Cl  H  H H  CH.sub.2                                                                             ##STR150##      191-192° C. (decomp.)        153 H  H H   H  H H  CH.sub.2                                                                             ##STR151##      120-121° C.                  154 H  H H   H  H H  CH.sub.2                                                                             ##STR152##      118-120° C.                  155 H  H Cl  H  H H  CH.sub.2                                                                             ##STR153##      191-192° C. (decomp.)        156 H  H H   H  H H  CH.sub.2                                                                             ##STR154##                                          157 H  H Cl  H  H H  CH.sub.2                                                                             ##STR155##                                          158 H  H H   H  H H  CH.sub.2                                                                             ##STR156##      158-159° C.                  159 H  H Cl  H  H H  CH.sub.2                                                                             ##STR157##                                          160 H  H H   H  H H  CH.sub.2                                                                             ##STR158##        115-117,5° C.              161 H  H H   H  H H  CH.sub.2                                                                             ##STR159##                                          162 H  H H   H  H H  CH.sub.2                                                                             ##STR160##      140-142° C.                  163 H  H Cl  H  H H  CH.sub.2                                                                             ##STR161##                                          164 H  H H   H  H H  CH.sub.2                                                                             ##STR162##                                          165 H  H H   H  H H  CH.sub.2                                                                             ##STR163##                                          166 H  H H   H  H H  CH.sub.2                                                                             ##STR164##      164-165° C.                  167 H  H H   H  H H  CH.sub.2                                                                             ##STR165##                                          168 H  H Cl  H  H H  CH.sub.2                                                                             ##STR166##                                          169 H  H H   H  H H  CH.sub.2                                                                             ##STR167##      129-132°C.                   170 H  H H   H  H H  CH.sub.2                                                                             ##STR168##        155-157,5° C.              171 H  H H   H  H H  CH.sub.2                                                                             ##STR169##                                          172 H  H H   H  H H  CH.sub.2                                                                             ##STR170##                                          173 H  H Cl  H  H H  CH.sub.2                                                                             ##STR171##                                          174 H  H H   H  H H  CH.sub.2                                                                             ##STR172##      158-160° C.                  175 H  H H   H  H H  CH.sub.2                                                                             ##STR173##                                          176 H  H Cl  H  H H  CH.sub.2                                                                             ##STR174##                                          177 H  H Cl  H  H H  CH.sub.2                                                                             ##STR175##      155-158° C. (decomp.)        178 H  H H   H  H H  CH.sub.2                                                                             ##STR176##                                          179 H  H H   H  H H  CH.sub.2                                                                             ##STR177##      144-146° C.                  180 H  H H   H  H H  CH.sub.2                                                                             ##STR178##                                          181 H  H H   H  H H  CH.sub.2                                                                             ##STR179##                                          182 H  H H   H  H H  CH.sub.2                                                                             ##STR180##      123-124° C.                  183 H  H H   H  H H  CH.sub.2                                                                             ##STR181##                                          184 H  H H   H  H H  CH.sub.2                                                                             ##STR182##                                          185 H  H H   H  H H  CH.sub.2                                                                             ##STR183##                                          186 H  H H   H  H H  CH.sub.2                                                                             ##STR184##      173-176° C. (decomp.)        187 H  H H   H  H H  CH.sub.2                                                                             ##STR185##                                          188 H  H H   H  H H  CH.sub.2                                                                             ##STR186##      134-136° C. (decomp.)        189 H  H H   H  H H  CH.sub.2                                                                             ##STR187##      100-102° C.                  190 H  H H   H  H H  CH.sub.2                                                                             ##STR188##                                          191 H  H H   H  H H  CH.sub.2                                                                             ##STR189##                                          192 H  H H   H  H H  CH.sub.2                                                                             ##STR190##      197-199° C.                  193 H  H Cl  H  H H  CH.sub.2                                                                             ##STR191##                                          194 H  H Cl  H  H H  CH.sub.2                                                                             ##STR192##                                          195 H  H H   H  H H  CH.sub.2                                                                             ##STR193##      170-171° C.                  __________________________________________________________________________

Formulation Examples for liquid active ingredients of the formula I (%=percent by weight)

    ______________________________________                                         4. Emulsion concentrates                                                                          (a)       (b)    (c)                                        ______________________________________                                         active ingredient from Table 1                                                                    25%       40%    50%                                        calcium dodecylbenzenesulfonate                                                                    5%        8%     6%                                        castor oil-polyethylene glycol                                                                     5%       --     --                                         ether (36 mols of ethylene oxide)                                              tributylphenol-polyethylene glycol                                                                --        12%     4%                                        ether (30 mols of ethylene oxide)                                              cyclohexanone      --        15%    20%                                        xylene mixture     65%       25%    20%                                        ______________________________________                                    

Emulsions of any required concentration can be produced from concentrates of this type by dilution with water.

    ______________________________________                                         5. Solutions       (a)     (b)    (c)   (d)                                    ______________________________________                                         active ingredient from Table 1                                                                    80%     10%    5%    95%                                    ethylene glycol-monomethyl ether                                                                  20%     --     --    --                                     polyethylene glycol M G 400                                                                       --      70%    --    --                                     N--methyl-2-pyrrolidone                                                                           --      20%    --    --                                     epoxidised coconut oil                                                                            --      --     1%     5%                                    ligroin (boiling limits 160-190° C.)                                                       --      --     94%   --                                     ______________________________________                                    

The solutions are suitable for application in the form of very fine drops.

    ______________________________________                                         6. Granulates         (a)     (b)                                              ______________________________________                                         active ingredient from Table 1                                                                       5%      10%                                              kaolin                94%     --                                               highly dispersed silicic acid                                                                        1%      --                                               attapulgite           --      90%                                              ______________________________________                                    

The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.

    ______________________________________                                         7. Dusts             (a)     (b)                                               ______________________________________                                         active ingredient from Table 1                                                                      2%      5%                                                highly dispersed silicic acid                                                                       1%      5%                                                talcum               97%     --                                                kaolin               --      90%                                               ______________________________________                                    

Ready-for-use dusts are obtained by the intimate mixing together of the carriers with the active ingredient.

Formulation Examples for solid active ingredients of the formula I (%=percent by weight)

    ______________________________________                                         8. Wettable powders   (a)     (b)    (c)                                       ______________________________________                                         active ingredient from Table 1                                                                       25%     50%    75%                                       sodium lignin sulfonate                                                                              5%       5%    --                                        sodium lauryl sulfate 3%      --      5%                                       sodium diisobutylnaphthalene sulfonate                                                               --       6%    10%                                       octylphenolpolyethylene glycol ether                                                                 --       2%    --                                        (7-8 mols of ethylene oxide)                                                   highly dispersed silicic acid                                                                        5%      10%    10%                                       kaolin                62%     27%    --                                        ______________________________________                                    

The active ingredient is well mixed with the additives and the mixture is thoroughly ground in a suitable mill. Wettable powders which can be diluted with water to give suspensions of the required concentration are obtained.

    ______________________________________                                         9. Emulsion concentrate                                                        ______________________________________                                         active ingredient from Table 1                                                                        10%                                                     octylphenol polyethylene glycol ether                                                                  3%                                                     (4-5 mols of ethylene oxide)                                                   calcium dodecylbenzenesulfonate                                                                        3%                                                     castor oil polyglycol ether                                                                            4%                                                     (35 mols of ethylene oxide)                                                    cyclohexanone          30%                                                     xylene mixture         50%                                                     ______________________________________                                    

Emulsions of the required concentration can be obtained from this concentrate by dilution with water.

    ______________________________________                                         10. Dusts             (a)    (b)                                               ______________________________________                                         active ingredient from Table 1                                                                        5%     8%                                               talcum                95%    --                                                kaolin                --     92%                                               ______________________________________                                    

Dusts ready for use are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.

    ______________________________________                                         11. Extruder granulate                                                         ______________________________________                                         active ingredient from Table 1                                                                      10%                                                       sodium lignin sulfonate                                                                              2%                                                       carboxymethylcellulose                                                                               1%                                                       kaolin               87%                                                       ______________________________________                                    

The active ingredient is mixed and ground with the additives, and the mixture is moistened with water. This mixture is extruded and subsequently dried in a stream of air.

    ______________________________________                                         12. Coated granulate                                                           ______________________________________                                         active ingredient from Table 1                                                                      3%                                                        polyethylene glycol (M G 200)                                                                       3%                                                        kaolin               94%                                                       ______________________________________                                    

The finely ground active ingredient is evenly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Dustfree coated granules are obtained in this manner.

    ______________________________________                                         13. Suspension concentrate                                                     ______________________________________                                         active ingredient from Table 1                                                                        40%                                                     ethylene glycol        10%                                                     nonylphenolpolyethylene glycol ether                                                                   6%                                                     (15 mols of ethylene oxide)                                                    sodium lignin sulfonate                                                                               10%                                                     carboxymethylcellulose  1%                                                     37% aqueous formaldehyde solution                                                                     0.2%                                                    silicone oil in the form of a                                                                         0.8%                                                    75% aqueous emulsion                                                           water                  32%                                                     ______________________________________                                    

The finely ground active ingredient is intimately mixed with the additives. There is thus obtained a suspension concentrate from which can be produced, by dilution with water, suspensions of the concentration required.

BIOLOGICAL EXAMPLES Example 14 Tank mixture in the post-emergence process in the case of barley and wheat

Barley and wheat seeds, respectively, are sown, in a greenhouse, in plastics pots each containing 0.5 liter of soil. After emergence of the plants to the 2- to 3-leaf stage, the substance to be tested as an antidote and also the herbicide 2-[4-(3,5-dichloropyridyl-2-oxy)-phenoxy]-propionic acid-2-propinyl ester are applied together as a tank mixture. The protective action of the antidote is estimated in percent 20 days after application. The plants treated with the herbicide alone and the completely untreated plants provided reference values. The results are summarised in the following Tables:

                  TABLE 2                                                          ______________________________________                                         Test results for barley                                                        Antidote  Antidote    Herbicide  Relative protec-                              compound No.                                                                             kg of AS*/ha                                                                               kg of AS/ha                                                                               tive action in %                              ______________________________________                                          7        0,5         0,5        38                                            13        0,5         0,5        25                                            ______________________________________                                          (*AS = active ingredient)                                                

                  TABLE 3                                                          ______________________________________                                         Test results for wheat                                                         Antidote  Antidote    Herbicide  Relative protec-                              compound No.                                                                             kg of AS/ha kg of AS/ha                                                                               tive action in %                              ______________________________________                                         1         1,5         0,75       38                                            2         1,5         0,75       50                                            3         1,5         0,75       50                                            4         1,5         0,75       38                                            5         1,5         0,75       50                                            6         1,5         0,75       50                                            7         1,5         0,75       38                                            8         1,5         0,75       50                                            9         1,5         0,75       25                                            10        1,5         0.75       50                                            11        1,5         0,75       50                                            12        1,5         0,75       50                                            13        1,5         0,75       50                                            15        1,5         0,75       50                                            19        1,5         0,75       38                                            ______________________________________                                    

Example 15 Seed swelling with rice; herbicide in the pre-emergence process

Rice seeds are soaked for 48 hours in solutions of the substance to be tested as antidote at a concentration of 100 ppm, and the seeds are then left to dry for about two hours until they no longer stick together. Plastics containers (length×width×height=25×17×12 cm) are filled to 2 cm below the top edge with sandy loam. The pre-swelled seeds are sown on the surface of the soil in each container, and only slightly covered with soil, the soil being maintained in a moist (not muddy) state. The herbicide 2-chloro-2',6'-diethyl-N-[2"-(n-propoxy)-ethyl]-acetanilide is then applied as a dilute solution to the surface of the soil. The water level is successively raised to correspond with the growth of the plants. The protective action of the antidote is estimated in percent 18 days after application of the herbicide. The plants treated with the herbicide alone and the completely untreated plants provide reference values. The results are summarised in the following Table:

                  TABLE 4                                                          ______________________________________                                         Antidote  Antidote  Herbicide   Relative protec-                               compound No.                                                                             ppm       kg of AS/ha tive action in %                               ______________________________________                                         1         100       0,25        50                                             8         100       0,25        38                                             ______________________________________                                    

Example 16 Tank mixture in the pre-emergence process on soya-bean seeds

Pots (upper diameter 6 cm) are filled with sandy loam, and soya-bean seeds of the "Hark" variety are sown. After the seeds have been covered with soil, the substance to be tested as antidote and the herbicide 4-amino-6-tertbutyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one are in dilute solution together sprayed as a tank mixture onto the surface of the soil. The protective action of the antidote is estimated in percent 21 days after application of the herbicide. The plants treated with the herbicide alone and the completely untreated plants serve as control plants. One result is shown in the following Table:

                  TABLE 5                                                          ______________________________________                                         Antidote  Antidote    Herbicide  Relative protec-                              compound No.                                                                             kg of AS/ha kg of AS/ha                                                                               tive action in %                              ______________________________________                                         17        1.5         0.75       38                                            ______________________________________                                    

Example 17 Seed dressing with maize: Herbicide in the post-emergence process

Maize seeds of the "LG 5" variety are placed together with the substance to be tested as antidote into a glass container, and well mixed by shaking and rotation. Plastics pots (upper diameter 11 cm) are filled with soil, and the dressed seeds are sown. After the seeds have been covered with soil, the herbicide N-[2-(2-butenyloxy)-phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea is applied in the post-emergence process. The protective action of the antidote is estimated in percent 18 days after application of the herbicide. The plants treated with the herbicide alone and the completely untreated plants serve as control plants. The results are summarised in the following Table:

                  TABLE 6                                                          ______________________________________                                         Herbicide                                                                      kg of AS/ha                                                                               1.5        1.0         0.5                                          ______________________________________                                         antidote    4     2      1   4    2   1    4   2    1                          compound No. 7                                                                 g of AS/kg                                                                     of seed                                                                        relative protec-                                                                          25    38     38  50   63  50   25  25   25                          tive action in %                                                               ______________________________________                                    

Example 18 Seed dressing with maize: herbicide in the pre-emergence process

Maize seeds of the "LG 5" variety are placed together with the substance to be tested as antidote into a glass container and they are well mixed by shaking and rotation. Plastics pots (upper diameter 11 cm) are filled with soil, and the dressed seeds are sown therein. After the seeds have been covered with soil, the herbicide N-[2-(2-butenyloxy)-phenyl-sulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea is applied in the pre-emergence process. The protective action of the antidote is estimated in percent 18 days after application of the herbicide. The plants treated with the herbicide alone and the completely untreated plants serve as control plants. One result is given in the following Table:

                  TABLE 7                                                          ______________________________________                                                   Antidote                                                             Antidote  g of AS/kg Herbicide   Relative protec-                              compound No.                                                                             of seed    kg of AS/ha tive action in %                              ______________________________________                                         7         1          1,0         25                                            ______________________________________                                    

Example 19 Seed dressing with barley:herbicide in the pre-emergence process

Barley seeds are placed together with the substance to be tested as antidote into a glass container, and the whole is well mixed by shaking and rotation. Plastics containers (length×width×height=25×17×12 cm) are filled with sandy loam, and the dressed seeds are sown therein. After the seeds have been covered with soil, the herbicide N-(2-chlorophenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea is sprayed onto the surface of the soil. The protective action of the antidote is estimated in percent 21 days after application of the herbicide. The plants treated with the herbicide alone and also the completely untreated control plants provide reference values. The results are summarised in the following Table:

                  TABLE 8                                                          ______________________________________                                                   Antidote                                                             Antidote  g of AS/kg Herbicide   Relative protec-                              compound No.                                                                             of seed    kg of AS/ha tive action in %                              ______________________________________                                         7         0,5        1,0         63                                                      0,25       1,0         63                                                      0,125      1,0         63                                            7         0,5        0,5         75                                                      0,25       0,5         75                                                      0,125      0,5         75                                            7         0,5         0,25       63                                                      0,25        0,25       75                                                      0,125       0,25       63                                            7         0,5         0,125      63                                                      0,25        0,125      63                                                      0,125       0,125      50                                            ______________________________________                                    

Example 20 Seed dressing (wheat): herbicide in the pre-emergence process

Wheat seeds are placed together with the substance to be tested as antidote into a glass container, and the whole is well mixed by shaking and rotation. Plastics containers (length×width×height=25×17×12 cm) are filled with sandy loam soil, and the dressed seeds are sown therein. After the seeds have been covered with soil, the herbicide N-(2-chlorophenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea is sprayed onto the surface of the soil. The protective action of the antidote is estimated in percent 21 days after application of the herbicide. The plants treated with the herbicide alone and also the completely untreated control plants provide reference data. The results are summarised in the following Table:

                  TABLE 9                                                          ______________________________________                                                   Antidote                                                             Antidote  g of AS/kg Herbicide   Relative protec-                              compound No.                                                                             of seed    kg of AS/ha tive action in %                              ______________________________________                                         7         1          1,5         38                                                      0,5        1,5         38                                                      1          1,0         25                                                      0,5        1,0         25                                            ______________________________________                                    

Example 21 Seed dressing (barley): herbicide in the post-emergence process

Barley seeds are placed together with the substance to be tested as antidote into a glass container, and the whole is well mixed by shaking and rotation. Plastics containers (length×width×height=25×17×12 cm) are filled with sandy loam soil, and the dressed seeds are sown therein. After the seeds have been covered with soil, the herbicide N-(2-chlorophenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea is applied in the post-emergence process. The protective action of the antidote is estimated in percent 21 days after application. The plants treated with the herbicide alone and also the completely untreated control plants provide reference data. The results are summarised in the following Table:

                  TABLE 10                                                         ______________________________________                                                   Antidote                                                             Antidote  g of AS/kg Herbicide   Relative protec-                              compound No.                                                                             of seed    kg of AS/ha tive action in %                              ______________________________________                                         7         2          1,5         50                                                      1          1,5         50                                                        0,5      1,5         63                                            7         2          1,0         63                                                      1          1,0         63                                                        0,5      1,0         63                                            7         2          0,5         38                                                      1          0,5         38                                                        0,5      0,5         38                                            ______________________________________                                    

Example 22 Seed dressing (wheat): herbicide in the post-emergence process

Wheat seeds are placed together with the substance to be tested as antidote into a glass container, and the whole is well mixed by shaking and rotation. Plastics containers (length×width×height=25×17×12 cm) are filled with sandy loam soil, and the dressed seeds are sown therein. After the seeds have been covered with soil, the herbicide N-(2-chlorophenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea is applied in the post-emergence process. The protective action of the antidote is estimated in percent 21 days after application of the herbicide. The plates treated with herbicide alone and also the completely untreated control plants provide reference values. The results are summarised in the following Table:

                  TABLE 11                                                         ______________________________________                                                   Antidote                                                             Antidote  g of AS/kg Herbicide   Relative protec-                              compound No.                                                                             of seed    kg of AS/ha tive action in %                              ______________________________________                                         7         1          1,0         25                                                      0,5        1,0         25                                            ______________________________________                                    

Example 23 Tank mixture in the post-emergence process on maize

Maize seeds of the "LG 5" variety are sown, in a greenhouse, in plastics pots (upper diameter 11 cm) each containing 0.5 liter of soil. After the seeds have been covered with soil, the substance to be tested as antidote and the herbicide N-[2-(2-butenyloxy)-phenyl-sulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea are applied together as a tank mixture in the post-emergence process. The protective action of the antidote is estimated in percent 18 days after application. The plants treated with herbicide alone and also the completely untreated control plants provide reference data. One reaction is shown in the following Table:

                  TABLE 12                                                         ______________________________________                                         Antidote  Antidote    Herbicide  Relative protec-                              compound No.                                                                             kg of AS/ha kg of AS/ha                                                                               tive action in %                              ______________________________________                                         7         1,0         1,0        38                                            ______________________________________                                    

Example 24 Seed dressing (rice): herbicide in the pre-emergence process

Rice seeds are placed together with the substance to be tested as antidote into a glass container, and the whole is well mixed by shaking and rotation. Containers (length×width×height=47×29×24 cm) are filled with sandy loam soil, and the dressed seeds are sown therein. After the seeds have been covered with soil, the herbicide 2-[4-(3,5-dichloropyridyl-2-oxy)-phenoxy]-propionic acid-2-propynyl ester is sprayed as a dilute solution onto the surface of the soil. Twenty days after sowing, when the plants have reached the 3-leaf stage, water is applied until the surface of the soil is covered by a layer of water 4 cm in height. The protective action of the antidote is estimated in percent 30 days after application of the herbicide. The plants treated with herbicide alone and also the completely untreated plants provide reference data. The results are summarised in the following Table:

                  TABLE 13                                                         ______________________________________                                                   Antidote                                                             Antidote  g of AS/kg Herbicide   Relative protec-                              compound No.                                                                             of seed    kg of AS/ha tive action in %                              ______________________________________                                         7         0,6        0,25        50                                                      0,3        0,25        50                                                      0,2        0,25        38                                            ______________________________________                                    

Example 25 Seed dressing (rice): herbicide in the pre-emergence process

Rice seeds of the IR-36 variety are placed together with the substance to be tested as antidote into a glass container, and the whole is well mixed by shaking and rotation. Plastics containers (length×width×height=47×29×24 cm) are filled with sandy loam soil, and the dressed seeds are sown therein. After the seeds have been covered with soil, the herbicide 2-[4-(3,5-dichloropyridyl-2-oxy)-phenoxy]-propionic acid-2-propynyl ester is sprayed onto the surface of the soil. The protective action of the antidote is estimated in percent 18 days after sowing. The plants treated with herbicide alone and also the completely untreated control plants provide reference data. The results are summarised in the following Table:

                  TABLE 14                                                         ______________________________________                                                   Antidote                                                             Antidote  g of AS/kg Herbicide   Relative protec-                              compound No.                                                                             of seed    kg of AS/ha tive action in %                              ______________________________________                                         7         0,6        0,25        50                                                      0,3        0,25        50                                                      0,2        0,25        38                                            ______________________________________                                    

Example 26 Tank mixture in the post-emergence process on wheat

Wheat seeds of the "Farnese" variety are sown, in a greenhouse, in plastics pots (upper diameter 11 cm) each containing 0.5 liter of soil. After the seeds have been covered with soil, the substance to be tested as antidote and the herbicide 2-chloro-4-trifluoromethylphenyl-3'-oxazolin-2'-yl-4'-nitrophenyl ether are applied together as a tank mixture in the post-emergence process. The protective action of the antidote is estimated in percent 20 days after after application. The plants treated with herbicide alone and the completely untreated control plants provide reference data. The results are summarised in the following Table:

                  TABLE 15                                                         ______________________________________                                         Antidote  Antidote    Herbicide  Relative protec-                              compound No.                                                                             kg of AS/ha kg of AS/ha                                                                               tive action in %                              ______________________________________                                         13        0,25        0,25       25                                                      0,125       0,25       25                                            13        0,25        0,125      25                                                      0,125       0,125      25                                                      0,062       0,125      25                                            ______________________________________                                    

Example 27 Tank mixture in the post-emergence process on wheat

Wheat seeds of the "Farnese" variety are sown, in a greenhouse, in plastics pots (upper diameter 11 cm) each containing 0.5 liter of soil. After the seeds have been covered with soil, the substance being tested as antidote and the herbicide 2-[4-(5-trifluoromethylpyridyl-2-oxy)-phenoxy]-propionic acid-n-butyl ester are applied as a tank mixture in the post-emergence process. The protective action of the antidote is estimated in percent 20 days after application. Plants treated with herbicide alone and completely untreated control plants provide reference data. One result is shown in the following Table:

                  TABLE 16                                                         ______________________________________                                         Antidote  Antidote    Herbicide  Relative protec-                              compound No                                                                              kg of AS/ha kg of As/ha                                                                               tive action in %                              ______________________________________                                         13        0,125       0,060      25                                            ______________________________________                                    

Example 28 Seed dressing (sorghum): herbicide in the pre-emergence process

Sorghum seeds of the "Funk G 623" variety are placed together with the substance to be tested as antidote into a glass container, and the whole is well mixed by shaking and rotation. Plastics pots (upper diameter 11 cm) are filled with soil, and the dressed seed in sown therein. After the seeds have been covered with soil, there is applied as herbicide, in the pre-emergence process, either N-(2-chlorophenylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea (A) or N-(2-methoxycarbonylphenylsulfonyl)-N'-4,6-dimethylpyrimidin-2-yl)-urea (B). The protective action of the antidote is estimated in percent 18 days after application of the herbicide. The plants treated with herbicide alone and also the completely untreated plants provide reference data. The results are summarised in the following Table:

                  TABLE 17                                                         ______________________________________                                         Herbicide    Antidote         Relative                                         Com-             Compound  kg of AS/kg                                                                             protective                                 pound kg of AS/ha                                                                               No.       of seed  action in %                                ______________________________________                                         A     0,062      7         2          12,5                                                                1        25                                                                      0,5    25                                         A     0,031      7         2        25                                                                    1        38                                                                      0,5    50                                         A     0,015      7         2        50                                                                    1        63                                                                      0,5    63                                         B     0,062      7         2        38                                                                    1        38                                                                      0,5    25                                         B     0,031      7         2        50                                                                    1        38                                                                      0,5    25                                         B     0,015      7         2        50                                                                    1        50                                                                      0,5    50                                         ______________________________________                                     

What is claimed is:
 1. A compound of the formula ##STR194## wherein R₁ ', R₂ ' and R₃ ' independently of one another are each hydrogen, halogen, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, nitro or cyano,R₄ ', R₅ ' and R₆ ' independently of one another are each hydrogen, halogen or C₁ -C₃ alkyl, A' is any one of the groups --CH₂ --, --CH₂ CH₂ -- or --CH(CH₃)--, and Z' is the group ##STR195## wherein E is R₇ which is C₁ -C₇ alkyl which is unsubstituted or substituted by halogen or C₁ -C₄ alkoxy, or R₇ is C₃ -C₆ -cycloalkyl, C₂ -C₄ alkenyl, phenyl which is unsubstituted or substituted by halogen, nitro or C₁ -C₃ alkyl, or R₇ is benzyl which is unsubstituted or substituted by halogen, nitro or C₁ -C₃ alkyl, or R₇ is a 5-membered heterocyclic ring which contains one or two hetero atoms from the group N, O and S and which is unsubstituted or substituted by halogen, including the agriculturally-acceptable acid addition salts and metal complexes thereof.
 2. A compound according to claim 1 wherein R₁ ' is hydrogen, chlorine, bromine, iodine or nitro; R₂ ' is hydrogen; R₃ ' is hydrogen, fluorine, chlorine, bromine, iodine, C₁ -C₃ alkyl or nitro; R₄ ' is hydrogen, bromine or methyl; R₅ ' is hydrogen; and R₆ ' is hydrogen or methyl.
 3. A compound according to claim 2 wherein R₁ ' is hydrogen, chlorine, bromine or iodine; R₃ ' is hydrogen, chlorine or nitro; and R₄ ' is hydrogen.
 4. A compound according to claim 3 wherein R₃ ' is hydrogen or chlorine and A' is --CH₂ --.
 5. O-(Chloromethylcarbonyl)-2-(8-quinolinoxy)-acetamide oxime accordng to claim
 4. 6. A compound of claim 1 wherein R₇ is a heterocyclic ring which is unsubstituted or substituted by halogen and which is selected from the group consisting of thiophene, furan and tetrahydrofuran.
 7. O-(2-furanylcarbonyl)-2-(5-chloro-8-quinolinoxy)-acetamide oxide according to claim
 6. 